N-heterocyclic perfluoroalkylmonocarboxylic acid esters, processes for their manufacture and their use

ABSTRACT

Perfluoroalkylmonocarboxylic acid esters from ethylene urea epoxides are provided. These esters contain a perfluoro alkyl radical, which is bonded directly or via an alkylene group with 1 to 10 carbon atoms to a carboxyl group. This carboxyl group is bonded in an ester-like manner to an acylic, aliphatic radical substituted in the 2-position to the ester bridge by a free, etherified or esterified hydroxyl group. This latter radical being bonded to a ring nitrogen atom of an ethylene urea radical, which in turn at least by its second ring nitrogen atom is bonded to an acylic aliphatic radical which contains an epoxide group in the terminal position or is linked to an acylic aliphatic radical which is in turn bonded in an esterlike manner to a perfluoroalkyl radical. These fluoro compounds are manufactured from the corresponding perfluoroalkylcarboxylic acids and epoxides and are used for finishing of porous and non-porous substrates, especially for producing oleophobic finishes on textiles.

United States Patent Jaeger 5] Nov. 18, 1975 1 N-HETEROCYCLIC 1,102,903 2/1968 United Kingdom PERFLUOROALKYLMONOCARBOXYLIC 2,058,999 6/1971 Germany 260/309.7

ACID ESTERS, PROCESSES FOR THEIR MANUFACTURE AND THEIR USE [75] Inventor: Horst Jaeger, Bettingen, Switzerland [73] Assignee: Ciba-Geigy AG, Basle, Switzerland [22] Filed: Feb. 6, 1973 [21] Appl. No.: 330,160

Related US. Application Data [60] Continuation-in-part of Ser. No. 286,797, Sept. 6, 1972, which is a division of Ser. No. 95,430, Dec. 4, 1970, abandoned.

[30] Foreign Application Priority Data Dec. 10, 1969 Switzerland 18400/69 Feb. 9, 1970 Switzerland 1827/70 [52] US. CL... 260/309.7; 117/139.5 R; 117/143 A; 117/161 UG; 260/2 A; 260/78.4 EP; 260/248 NS; 260/251 R [51] Int. C1. C07D 233/34 [58] Field of Search 260/309.7

[56] References Cited UNITED STATES PATENTS 3,014,042 12/1961 Mantz 260/309.7 3,209,010 9/1965 Gagliardi et a1. 260/309.7 3,248,399 4/1966 Walles et a1. 260/309.7 3,365,426 l/1968 Walles 260/309.7 3,429,833 2/1969 Porret 260/2 3,745,169 7/1973 Ogden 260/309.7

FOREIGN PATENTS OR APPLICATIONS 1,096,392 12/1967 United Kingdom OTHER PUBLICATIONS Malinovskii, Epoxides And Their Derivatives, p. 185, Daniel Davey and Co., Inc., NY (1965 Primary ExaminerJohn D. Randolph Attorney, Agent, or Firm-Joseph G. Kolodny; Prabodh I. Almaula; Edward McC. Roberts [57] ABSTRACT Perfluoroalkylmonocarboxylic acid esters from ethylene urea epoxides are provided. These esters contain a perfluoro alkyl radical, which is bonded directly or via an alkylene group with 1 to 10 carbon atoms to a carboxyl group. This carboxyl group is bonded in an ester-like manner to an acylic, aliphatic radical substituted in the 2-position to the ester bridge by a free, etherified or esterified hydroxyl group. This latter radical being bonded to a ring nitrogen atom of an ethylene urea radical, which in turn at least by its second ring nitrogen atom is bonded to an acylic aliphatic radical which contains an epoxide group in the terminal position or is linked to an acylic aliphatic radical which is in turn bonded in an esterlike manner to a perfluoroalkyl radical. These fluoro compounds are manufactured from the corresponding perfluoroalkylcarboxylic acids and epoxides and are used for finishing of porous and non-porous substrates, especially for producing oleophobic finishes on textiles.

12 Claims, No Drawings N-HETEROCYCLIC PERFLUOROALKYLMONOCARBOXYLICACID ESTERS, PROCESSES FOR THEIR 1 MANUFACTURE AND THEIR USE 5 This is a continuation-in-part of applicants co-pending application Ser. No. 286,797, filed Sept. 6, 1972, which, in turn, is a division of application Ser. No.

95,430, filed Dec. 4, 1970, now abandoned. 10

radical as defined under (b), which is in turn bonded in an esterlike manner to a radical as defined under (a).

The alkylene group via which the perfluoroalkyl radical can be bonded to the carboxyl group can be linear or cyclic. Thus one is concerned, for example, with cycloalkylene radicals with 5 or 6 ring carbon atoms, such as the cyclohexylene radical, or especially with n-alkylene radicals with 1 to 10 carbon atoms.

The perfluoroalkylmonocarboxylic acid esters preferably correspond to the formula wherein R and R each represent a perfluoroalkyl radical with 4 to 14 carbon atoms, E and E each represent a cycloalkylene radical with 5 or 6 ring carbon atoms or an n-alkylene radical with l to 10 carbon atoms, X and X each represent a methyl group or preferably a hydrogen atom, Y and Y each represent a hydrogen atom or preferably a methyl group, A and A' each represent a radical of the formula being bonded to (c) a ring nitrogen atom of a S-membered N-heterocyclic radical containing at least two wherein R, E", X" and Y" have the meaning indicated for R, E, X and Y and m, n, p, q, r, s, x, y and ring nitrogen atoms, this heterocyclic radical being in. 60 2' each are l or 2, and Z to Z each denote a hydrogen turn bonded, at least by its second ring nitrogen atom, (l) to an acylic aliphatic radical which contains an epoxide group in the terminal position or (2) linked to a atom or an alkyl radical with l to 4 carbon atoms.

esters correspond to the formula m-l O pl CH,---c- 0] wherein R, R, X, X, Y, Y, m, n, p and q have the indi- In the case where A or A represents the unit recated meaning, A and A each denote a radical of the quired to make up a triazine ring, the compound of formula (1 can contain yet further perfiuoroalkyland x, y and z each denote an integer having a value of monocarboxylic acid esters, provided r is 2.

l to l l. x, y and z are preferably integers having a value of 1 In the case of five-membered rings, the radicals Z to to 3, or especially 1.

2, preferably represent hydrogen atoms, whereas in the If x, y and z are greater than 1, they preferably reprecase of six-membered rings at least one of the radicals 40 sent integers having a value of 3 to 5.

Z, to Z preferably represents an alkyl radical with 1 to Particular interest attaches to perfluoroalkylmonocarboxylic acid esters of the formula 4 carbon atoms.

RCOO C HC-Y l: Y CH 1? I HO CH2 I O nl O m I o ml l I? CH ,C o -c H2 1 2- Where q is 2, the comounds of formula (1) are N- wherein R, X, Y, A, A, m, n and q have the meaning heterocyclic esters with at least two perfluoroalkylindicated. monocarboxylic acid groups, and if q is 1, the com- Particularly suitable perfluoroalkylmonocarboxylic pounds are esters with at least one perfluoroalkylacid esters correspond to the formula monocarboxylic acid group.

wherein A denotes a radical of the formula Perfluoroalkylmonocarboxylicacid esters of the formula with 2 to Z each representing a methyl group or es- RCOO CH 0 O I m-l I m-l O HO CH-CH CH HC pecially a hydrogen atom, and R, m, n and q having the wherein A represents a radical of the formula meaning indicated.

30 Suitable perfluoroalkylmonocarboxylic acid esters CH which are derived from s-triazines correspond to the H CH C CH formula I 2- or o=ci l a CH, H

m-l g V wherein R, X, Y and m have the meaning indicated.

As in the case of the compounds of formulae (2) and R (3) Y here again preferably represents a methyl group and m, n and q have the meaning indicated, lay claim d X h d t 50 to particular an a y rogen a Om Perfluoroalkylmonocarboxylic acid esters of the formula coo CH CH A CH H C OOC-R [R 1 I 2 L I J 1 2 L J 1 2 X HO -Cl-i--CH 0-CH-CH2 N N CH2- H-O CH,-H

m-l m-l or of the formula wherein R, m, q and A have the meaning indicated, are here preferred.

The perfluoroalkyl radical of the perfluoroalkylmonocarboxylic acid esters according to the invention preferably contains 5 to l 1, or especially 7 to 9, carbon atoms. The perfluoroalkyl radical can be either branched or unbranched, that is to say iso-perfluoroalkyl radicals, for example of the formula wherein n represents an integer having a value of 1 to l 1, can also be present. However, n-perfluoroalkyl rad monocarboxylic acid with 4. to 14 carbon atoms in the perfluoroalkyl radical, which is bonded directlyor via an alkylene bridge with 1 to 10 carbon atomsto the carboxyl group, with (2) at least one N-heterocyclic, S-membered or 6-membered epoxide containing at least 2 ring nitrogen atoms, which are each bonded to an epoxide group via an acyclic, aliphatic radical, and (3) subsequently optionally etherifying or esterifying the hydroxyl groups produced in this reaction with an alkanol or an alkylcarboxylic acid, respectively.

Depending on the molar ratio, -compounds are thereby obtained which contain one, two or, where relevent, three perfluoroalkylmonocarboxylic acid esters in the molecule. I

The reaction temperature is between 20 and 100C,

preferably between 20 and 70C. To manufacture perfluoroalkylcarboxylic acid esters which possess an alkylene group between the perfluoroalkyl radical and T C-CH,

Y m-l g the carboxyl group, it is advisable to carry out the process at to C. To manufacture corresponding compounds without an alkylene group, temperatures of 20 to 40C as a rule suffice. Depending on the reaction temperature and the reactivity of the reactants, the reaction takes 1 to 24 hours, but is in general complete after 4 to 8 hours. Preferably, the reaction is allowed to take place in the presence of a catalyst, such as for example anhydrous sodium acetate. The reaction is appropriately carried out in a solvent, such as for example ethyl acetate.

The new perfluoroalkylmonocarboxylic acid esters of formula (1) are accordingly advantageously manufactured by reacting at least one perfluoroalkylmonocarboxylic acid of formula (11) R(E) ,COOH as component (1) with an epoxide for formula I Y p-l O In these formulae,A, A and n have the meaning indicated.

The preparation of the particularly interesting per- 3, or especially 1.

CH2-CH2 9, carbon atoms, is achieved by reacting a perfluoroalkylmonocarboxylic acid having 5 to 11, preferably 7 to 9, carbon atoms in the perfluoroalkyl radical, with the fluoroalkylmonocarboxylic acid esters of which the 55 component (2). In formula (10), x is preferably 1, 2 or perfluoroalkyl radical contains 5 to l 1, preferably 7 to The epoxides used for the manufacture of the perfluoroalkylmonocarboxylic acid esters according to the invention are known and are manufactured according to methods which are in themselves known, by reacting the corresponding N-heterocyclic compound with an epihalogenohydrin, for example epichlorohydrin or B- methylepichlorohydrin.

As a result of the presence of free hydroxyl groups, the perfluoroalkylmonocarboxylic acid esters according to the invention react with compounds which contain several functional groups capable of reaction with hydroxyl groups, such as l,2-epoxide groups, isocyanate groups, acrylyl groups, methylol groups, methylol groups etherified with lower alcohols, aldehyde groups, easily hydrolysable ester groups, amino groups and the like. Such polyfunctional compounds are, therefore, suitable for use as crosslinking components or curing components for the perfluoroalkylmonocarboxylic acid esters, according to the invention, that contain hydroxyl groups.

As such crosslinking components there may especially be mentioned:

Epoxide compounds, especially polyglycidyl ethers, such as butanediol diglycidyl ether and diglycidyl ether, diisocyanates and polyisocyanates, such as mand p-phenylenediisocyanate, toluylene-Z,4-diisocyanate and l,S-naphthylenediisocyanate; acrylyl compounds such as methylenebisacrylamide and symmetrical triacrylylperhydrotriazine; poly-(2,3di-hydro-1,4-pyranyl) compounds, such as (2,3-dihydro-l ',4'-'pyran-2-yl)- methyl ester; aldehydes, such as formaldehyde or glyoxal, and soluble phenol-formaldehyde condensation products, such as novolaks or resols. Aminoplasts that are soluble in water or in organic solvents are preferably used as crosslinking components.

Possible aminoplasts are formaldehyde condensation products of urea, thiourea, guanidine, ethyleneurea, glyoxalmonourein, acetylenediurea and dicyandiamide, and also of arninotriazines, such as melamine, or of guanamines, such as acetoguanamine, benzoguanamine, tetrahydrobenzoguanamine or formoguanamine, as well as their ethers with alcohols, such as methyl, ethyl, propyl, allyl, butyl, amyl and hexyl alcohol, cyclohexanol, benzyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol or abietyl alcohol. In addition to the ether radicals, the condensation products can also contain radicals of higher-molecular acids, such as for example stearic acid.

Particularly good technical results in the field of textile finishing are obtained on using water-soluble condensation products of formaldehyde and melamine, or especially the esterification product or etherification product from hexamethanolmelamine-methyl-ethers and stearic acid or stearyl alcohol, as crosslinking components, for example hexamethanolmelamine-pentamethyl-ether, since an oleophobic effect and a hydrophobic effect can thus be simultaneously achieved. It is frequently also advantageous to employ the perfluoroalkylmonocarboxylic acid esters as precondensates with crosslinking agents, for example amines or aminoplast precondensates.

The perfluoroalkylmonocarboxylic acid esters can also be used as a mixture with polymers not containing fluorine. Polymers not containing fluorine which are very suitable are here, for example, the homopolymers of acrylic acid esters or methacrylic acid esters, such as poly(ethyl acrylate) or copolymers of acrylic acid esters or methacrylic acid esters with methylolacrylamide or methylolmethacrylamide. I

The perfluoroalkylmonocarboxylic acid esters according to the invention can, by virtue of their reactive groupings, be used for the treatment of porous and non-porous substrates, preferably for producing oleophobic finishes thereon, it being possible to incorporate the esters into the material in question or above all to apply them to its surface. By porous substrates, leather or preferably fibre materials such as textiles and paper are to be understood; possible non-porous materials are plastics and above all surfaces of metals and glass.

The finishing of the substrate with the perfluoroalkylmonocarboxylic acid esters according to the invention can be carried out in a process step by itself, but also in the same process step as the application of further finishing agents, for example together with known agents for imparting hydrophobic properties, such as, paraffin emulsions, or solutions or emulsions of fatty acid condensation products, for example with amino-plast precondensates, and as mentioned above.

Further, a so-called soil release and anti-soiling effect can also be achieved with the perfluoro compounds according to the invention, especially on cotton.

At the same time as imparting oleophobic properties, these perfluoro compounds also show hydrophilic properties. For rendering oleophobic, the substrates can be treated either with solutions or with dispersions or emulsions of the perfluoro compounds. Perfluoroalkylmonocarboxylic acid esters can, for example, also be applied to the textile material in a solution with an organic solvent, and be heat-fixed to the fabric after evaporation of the solvent.

Particular interest as regards finishing by means of the perfluoroalkylmonocarboxylic acid esters according to the invention attaches to textile materials. Examples of such materials include those from native or regenerated cellulose, such as cotton, linen or rayon, viscose staple, or cellulose acetate. However, textiles made of wool, synthetic polyamides, polyesters or polyacrylonitrile can also be used. Mixed woven fabrics or mixed knitted fabrics of cotton-polyester fibres can also advantageously be finished. The textiles can here be in the form of filaments, fibres or flocks, but preferably of woven fabrics or knitted fabrics.

Preparations which contain the perfluoro compound according to the invention can be applied to the substrate in the customary manner which is in itself known. Woven fabrics can for example be impregnated according to the exhaustion process, or on a padder which is fed with the preparation at room temperature. The impregnated material is thereafter dried at 60 to C and subsequently, where appropriate, also subjected to 17 a heat treatment at above 100C, for example at 120 to 200C.

The textiles treated in this way as a rule show an oilrepellent action, and where the preparation also contains an agent for conferring hydrophobic properties, this action is coupled with a water-repellent action.

EXAMPLE 1 32 g of diglycidyl-ethyleneurea and 41.4 g of perfluorocaprylic acid are dissolved in 10 ml of distilled water, which is mixed with 30 ml of ethyl acetate, at room temperature, with the addition of 2 g of anhydrous sodium acetate.

The temperature rises to 33C and the reaction temperature is kept constant at 40C. After 6 hours reaction the epoxide content is 18.3%, relative to the expected end product. The solution is concentrated in vacuo at 40C. The residue is taken up in 100 ml of acetone and dried with Na SO The supernatant solution is filtered off and concentrated in vacuo at 40C, and yields a light brown, highly fluid phase. Weight 73.4 g 100% of theory.

Recording a mass spectrum confirms the structure, in that it shows a molecular weight of 612, which corre- (lll) sponds to a product of the formula 16 g of diglycidyl-ethyleneurea and 41.4 g of perfluorocaprylic acid are dissolved in 5 ml of distilled water, which is mixed with 30 ml of ethyl acetate, at room temperature, with the addition of 2.0 g of anhydrous sodium acetate.

The temperature rises to 32C, and the reaction temperature is kept constant at-40C. After 7 hours reaction, the epoxide content is 0%. The solution is concentrated in vacuo at 40C. The residue is taken up in 300 ml of acetone and dried with Na SO The supernatant solution is filtered off and concentrated in vacuo at 40C, and yields a light brown, highly fluid phase. Weight 57.0 g 100% of theory.

Recording a mass spectrum confirms the structure, in that it shows a molecular weight of 1026, which corresponds to a product of the formula EXAMPLE 3 40 g of diglycidyl-ethyleneurea of the formula (20.1 and 100 g of perfluoroalkylalkylcarboxylic acid* are dissolved in 200 ml of ethyl acetate at room temperature, with the addition of 2 g of anhydrous sodium acetate.

* )The perfluoroalkylalkylcarboxylic acid used has the following composition according to a gas chromatogram and mass spectrum:

4.5 c r cancoon M 420 9 c,.F,,c,H,,cooH M 520 3 c,.,F,,c,H,.cooH M 620 The parent peaks 718 and 818 which would correspond to the products with w 4; u 7.9, are not visible in the mass spectrum recording of this mixture.

EXAMPLE 4 40 g of diglycidyl-ethyleneurea of the formula (20.1) and 100 g of perfluoroalkylalkylcarboxylic acid* are dissolved in 200 ml of ethyl acetate at room temperature, with the addition of 2 g of anhydrous sodium acetate.

*)The perfluoroalkylalkylcarboxylic acid used has the following composition according to a gas chromatogram and mass spectrum:

19 C F C H COOH M 492 40.5 7: C, F- C H,COOH M 592 20 C F C H COOH M 520 15 7c C ,F ,C H COOH M 620 The reaction temperature is kept constant at C. After 6 hours reaction the epoxide content is 59.3 relative to 1 epoxy group. The solution is diluted with absolute ethanol, filtered andconcentrated in vacuo at 40C. The residue is water-soluble and gives a weight of 132 g 94.3 of theory.

Recoridng a mass spectrum conforms the structure, in that it shows molecular weights of 690, 790, 718 and 818, which corresponds to a product of the formula OH C EXAMPLE 40 g of diglycidyl-ethyleneurea of the formula(20.l) and 100 g of perfluoroalkylalkylcarboxylic acid* are dissolved in 350 ml of ethyl acetate at room temperature, with the addition of 2 g of anhydrous sodium acetate.

*)The perfluoroalkylalkylcurboxylic acid used has the following composition according to a gas chromatogram and mass spectrum:

l6 7! CF;,(C 2)9(CH COOH 3 7c CF;,(CF (CH COOH M 692 7c CF;,(CF (CH COOH M 420 CF -,(C Z)T(CH COOH M 520 M 790 (u=9;w=2) M746 (u=7;w=6) The part A is partially crosslinked.

Weight A 59.3 g A 32.4 7? of epoxide relative to one Weight B 79 A90 of epoxide epoxy group.

Recording a mass spectrum of the part B confirms the structure, in that it shows a molecular weight of which corresponds to a product of the formula (V) CH CH EXAMPLE 6 5.5 g of diglycidyl-ethyleneurea of the formula( 20. l) and 16.5 g of perfluoroalkylalkylcarboxylic acid* are dissolved in 100 ml of ethyl acetate at room temperature, with the addition of l g of anhydrous sodium acetate.

* )The perfluoroalkylalkylcarboxylic acid used had the following composition, according to a gas chromatogram and mass spectrum: l0 7: C F C H COOH M 492 28 7t C F CJ-LCOOH M 592 30 7c C F C I-LCOOH M 692 30 7: C F C H COOH M 792 The reaction temperature is kept constant at C. After 7 hours reaction the epoxide content is 94 The solution is concentrated in vacuo at 70C and yields a light yellow, solid phase. Weight 21.9 g of theory. I

Recording a mass spectrum confirms the structure, in that it shows molecular weights of 690 to 990, which corresponds to a product of the formula u=7 l3,w=2.

EXAMPLE 7 40 g of diglycidyl-ethyleneurea of the formula (20.1 and g of perfluoroalkylalkylcarboxylic acid* are dissolved in 350 ml of ethyl acetate at room temperature, with the addition of 2 g of anhydrous sodium acetate.

*)The perfluoroalkylalkylcarboxylic acid used has the following composition according to a gas chromatogram and mass spectrum:

30 C F C H COOH M 5 4 50 C F C H COOH M 604 20 C F C H COOH M 704 The reaction temperature is kept constant at 80C. After 12 hours reaction the epoxide content is 85 The solution is concentrated in vacuo at 70C, and yields a light brown, semi-solid phase. Weight g 81.25 of theory.

Recording a mass spectrum conforms the structure, in that it shows a molecular weight of 702 to 902, which corresponds to a product of the formula 3,920,689 21 22 vi!) CHQQCHZ u 5, 7, 9 w ID The reaction'temperature is kept constant at 75C. EXAMPLE 8 g l After 7 hours reaction, the epoxide content is 52.0 40 g of diglycidyl-ethyleneurea of the formula (20.1 relative to 1 epoxy group. The solution is filtered and and 111 g of perfluoroalkylcycloalkylcarboxylic acid concentrated in vacuo at 40C. The residue is a yellow, are dissolved in 400 ml of ethyl acetate at room temhighly viscous substance which is water-soluble. Yield perature, with the addition of 2 g of anhydrous sodium l40 g 86.4 of theory. acetate. The reaction temperature is kept constant at 15 Analysis: F (calculated) 40.07. (found) 38.75. 80C. After 10 hours reaction the epoxide content is The reaction product corresponds to the formula:

GH -CH CF;,(CF2).,CH2CH2C0OCH CHCH OCHCH -N N-CH CHOCH CHCH 2 OH CH; fi CH u=59 70%. The solution is concentrated in vacuo at 70C EXAMPLE l0 7 and yields a yellow, solid phase. Weight l25 g 82.7 31 g of NNI dipmpylene diglycidyl ether ethy|en;

them" urea of the formula is (m 2, A2 -CH2CH2) Recording a mass spectrum confirms the structure, in and 100 g of perfluoroalkyalkylcarboxylic acid** are that it shows a molecular weight of 644 to 844, which dissolved in 200 ml of ethyl acetate at room temperacorresponds to a product of the formula ture, with the addition of 2 g of anhydrous sodium acetate.

(VIII) cu "CH 7 2 2 (TF CF ll CI-i-C'i --I-.' ii--CH CH-CH, 2 2 2 'l'he perfluoroalkylcycloalkylcarboxylic acid used has the following Th ti temperature i k t t t 75C composition according to a gas chromatogram and mass spectrum. After 7 hours, reaction, the epoxide content is 0 The solution is filtered and concentrated in vacuo at 40C. 28 CBFI COOH M The residue is a yellow, highly viscous substance which I is water-soluble. Yield 105 g 80.15 of theory. 49 7 C F Analysis: F (calculated) 48.23. (found) 47.1. n COOH M 546 The reaction product corresponds to the formula:

CH2CH2 CF -,(CF CH cH COOCH,(fH-CH,OCHCH,K /NCH CHOCH Cl-l-CH OOCCH CH (CF ),,CF=,

' 0H CH C CH OH 18.5 c..,F,, I v

-C0OH M 646 EXAMPLE ll 43 g of N,N'-diglycidyl-4-methyl-ethylene ureea of EXAMPLE 9 the formula (20.2) and 82 g of perfluorocaprylic acid are dissolved in 200 ml of ethyl acetate at room temg: fif perature, with the addition of 2 g of anhydrous sodium and 100 g of perfluoroalkyalkylcarboxylic acid** are acetatedissolved in 200 ml of ethyl acetate at room temper- The reaction temperature is kept constant at C.

ture, with the addition of 2 g of anhydrous sodium ace- After 7 hours reaction, the epoxide content is 23 reltate. ative to l epoxy group. The solution is filtered and concentrated in vacuo at 40C. The residue is a yellow, lic acid*** are dissolved in 200 ml of ethyl acetate at highly viscous substance which is water-soluble. room temperature, with the addition of 2 g of anhy- Weight 97 g 77.6 of theory. drous sodium acetate.

Analysis: F (calculated) 45.53. (found) 44.3. The reaction temperature is kept constant at 75C. The reaction product corresponds to the formula: After 7 hours reaction, the epoxide content is 56.3

relative to 1 epoxy group. The solution is filtered and concentrated in vacuo at 40C. The residue is a yellow,

CH-CHCH,

l l highly viscous substance which is water-soluble. Yield f- {7 113,6 g 81.7 of theory.

Analysis: F (calculated) 46.81. (found) 46.0.

' The reaction product corresponds to the formula:

31 g of N,N-dipropylene-diglycidyl-ether-ethylene urea of the formula (18) (n1 2, A CH CH II and 82 g of perfluorocaprylic acid are dissolved in 200 0 ml of ethyl acetate at room temperature, withthe addition of 2 g of anhydrous sodium acetate. 30 u 5 9 The reaction tem erature is ke t constant at 75C. After 7 hours reacti t m, the epoxidg content is 0 The EXAMPLE solution is filtered and concentrated in vacuo at 40C. 21,5 g of N,N-diglycidyl-4-methyl-ethylene urea of The residue is a yellow, highly viscous substance which the fomiula (20.2) and 100 g of perfluoroalkylalkylcaris water-soluble. Yield, 87 g 77,2 of theory. boxylic acid"f** are dissolved in 200 ml of ethyl Analysis: F (calculated) 49.91. (found) 47.5. acetate at room temperature, with the addition of 2 g The. reaction product corresponds to the formula of anhydrous sodium acetate.

The reaction temperature is kept constant at 75C.

EXAMPLE 13 After 7 hours reaction, the epoxide content is 0 The 21,5 g of N,N-diglycidyl-4-methyl-ethylene urea of solution is filtered and concentrated in vacuo at C.

the formula (20.2) and 82 g of perfluorocaprylic acid The residue is a yellow, highly viscous substance which are dissolved in 200 ml of ethyl acetate at room tem- 40 is water-soluble. Weight 95 g 78.2 of theory.

perature, with the addition of 2 g of anhydrous sodium Analysis: F (calculated) 58.94. (found) 57.0. The reaction product corresponds to the formula:

The reaction temperature is kept constant at 75C. 11 5 9 After 7 hours reaction, the epoxide content is O The Composition of the .perfluoroalkylmonocarboxylic solution is filtered and concentrated in vacuo at 40C. acids: The residue is a yellow, highly viscous substance which is water-soluble. Yield 82 g 78.8 of theory. H CHCFZLCHZCHzCOOH Analysis: F (calculated) 54.80. (found) 54,0. The reaction product corresponds to the formula: 3; 9

43 g N,N-diglycidyl-4-methyl-ethylene urea of the 3:; 32:33:

formula (20.2) and 96 g of perfluoroalkylalkylcarboxyu 9 24.7 '7;

-continued and small amounts with u 9.

EXAMPLE 16 Liquors of the following composition are prepared with the products of the formulae (I) and (II).

Table Constituents Liquor HME hexamethylolmelamin-pentarnethyl ether Pieces of fabric of cotton, cotton-polyester, synthetic polyamide, polyester and wool gaberdine are successively dipped into this liquor and thus impregnated with the perfluoro compound.

A glass plate is also coated with these liquors. The fabric samples and glass samples are thereafter dried for minutes at 140C in vacuo.

The assessment of the oil-repellent effect is carried out according to the so-called 3M oil repellency test (Crajech and Petersen, Textile Research Journal 32, page 320 to 331 (1960)) using heptane-Nujol mixtures. In the assessment, 150 denotes the best obtainable rating. The individual samples are assessed immediately after drying, that is to say as they are, and after washing in boiling trichloroethylene for 5 minutes.

Table II Substrate Rating Achieved with Liquors E F G H Cotton: As obtained 120 100 70 120 after l X TCE 110 60 60 60 CottomPolyester: As obtained 130 120 100' 140 after 1 X TCE 1 60 80 80 Polyester: As obtained 140 130 110 120 after 1 X TCE 110 110 70 80 Polyamide: As obtained l 10 130 120 120 after 1 X TCE 120 110 80 80 Wool gabardine: As obtained 1 10 80 100 120 after l X TCE 9O 50 5O 50 Glass: As obtained 150 130 The finishes are oleophobic and hi ho hi ho after 1 X TCE after one wash in trichloroethylene hi hydrophilic ho hydrophobic EXAMPLE 17 3 g of a paraffin emulsion (containing 10 parts of a condensation product from hexamethylolmelaminehexamethyl-ether, stearic acid and stearic acid diglycidide, 10 parts of paraffin wasx and 18 parts of a con- 26 densation product of hexamethylolmelamine-hexamethylfether, stearic acid and triethanolamine) 6 g of a 50% strength solution of 1 mol of hexamethylolmelaminehexamethyl-ether and 1 mol of dimethylolethyleneurea, 0.1 g of AlCl a H 0 and 0.75 g of acetic acid are emulsified in ml of water.

The following are additionally emulsified in the solution:

6 g of the end product according to Example 1, dissolved in 10 ml of water.

Pieces of fabric of cotton, cotton-polyester, synthetic polyamide, polyester and Wool gabardine are successively dipped into these liquors and thus impregnated with the perfluoro compound.

The fabric are thereafter dried for 5 minutes at 130 C. The assessment of the oil-repellent effect is carried out as in Example 16.

The results are summarised in the table which follows:

a. 130 g of substance of the formula (11) are dissolved in 120 ml of ethyl acetate, and 10 g of triethylenetetramine, dissolved in 20 ml of ethyl acetate, are added dropwise at room temperature.

The mixture is stirred for 4 hours at 70 C. Thereafter the ethyl acetate is distilled off under a vacuum from a water pump, in the process of which a highly viscous, light yellow substance is obtained. This substance is dissolved in 300 ml of diethyl ether and the unreacted triethylenetetramine is eluted with two 20 ml portions of water. The residue is freed of ether and yields 141.0 g of a viscous, yellow substance.

b. to c. The following mixtures are warmed to 70 C for 15 to 20 minutes, so that a clear yellow solution is obtained:

Constituents Solution Substance of the formula (11) 56 61 Hexamethylolmelaminepentamethyl-ether g 35 3O Methanol ml 100 Yield g 93 70 The clear yellow solution is kept for a further 3 hours at 70 C and is cooled, and any methanol present is removed in vacuo; a highly viscous yellow substance is left, which is soluble in water.

The substances obtained according to Example 18 (a) to (c) are used in liquors of the following composition (concentrations in g/l):

Product from Example 18 a) 6 60 -cont1nued A B E F G r H J Product from Example 18 b) 20 30 Product from Example 18 c) 2O 30 30 Water to make up to ml 1000 1000 1000 I000 I000 acetone

Acetic acid 7: strenght 10 10 4 Hexamethylolmelamine-pentamethyl- 80 80 ether Paraffin emulsion according to 40 4O 40 4O 40 Example 18 AlCl X 6 H 0 2 2 Pieces of fabric of cotton, cotton-polyester, synthetic polyamide, polyester and wool gaberdine are succes- Pieces of fabric of cotton-polyester, synthetic polyamide, polyester and wool gaberdine are successively sively dipped into this liquor and thus impregnated with 20 dipped into these liquors and thus impregnated with the the perfluoro compound.

The fabrics are thereafter dried for 5 minutes at 130C.

The assessment of the oil-repellent effect is carried perfluoro compound.

The fabrics are thereafter dried for 5 minutes at The assessment of the oil-repellent effect is carried out as indicated in Example 16. Additionally, the samout as indicated in Example 16. However, instead of ples are also assessed after a SNV-3 wash (SNV-3 wash: wash in a bath containing 5 g of soap and 2 g of sodium carbonate per liter, for minutes at C).

The ratings achieved are given in the table which follows.

washing with trichloroethylene, the fabrics are subjected to l, 5 and 10 SNV-3 washes (compare Example 18). At the same time, the polyester/cotton fabrics were also tested for their soil release, again after 1, 5

30 and 10 SNV-3 washes. The test was here carried out ac- Substrate Rating achieved with Liquors B E F G H I co'm'm'; as obtained 100 100 so i so 90 6O 50 l X SNV 3 50 5O 50 5O Cotton/polyester as Obtained 100 100 I00 50 100 50 l XSNV 3 5O 5O 5O 50 Polyester. as obtained 9C 50 50 50 l X SNV 3 5O 90 l X Trichloroethylene Polyamide. as obtained 50 90 60 70 l X SNV 3 50 50 Wool gahardinc. as obtained 60 50 100 60 50 l X SNV 3 50 cording to the so-called stain release test method EXAMPLE 19 50 AATCC (1969).

The following liquors are prepared with the substances manufactured according to the instructions in Examples 4 to 8.

All fabrics proved to have simultaneously an oleophobic and a hydrophilic finish.

Product from D E F l *l 50% strength aqueous solution of hexamethylolmelamine hexamethyl-eslher and Llimethylolethylencurea Substrate D E r 1 K L M i N 's T L: v

Cotton as obtained v70 80 100 120 120 120 120 110 120 120 100 100 1 SNV3 120 120 110 110 110 x SNV 3 v 110 120 90 90 110 IOXSNV 3 100 110 110 Cotton/polyester as obtained 7O I20 120 1 x SNV 3 70 120 120 sxsNv 3 70 110 110 80 100 100 x SNV 3 100 110 80 Cotton Polyester Soil Release (Best Rating 5 A. Nujol as obtained. 1 x SNV 3 4 5 5 4.5 4.5 4.5 5 x SNV 2.5 2 2.3 4.5 5 4.8 4.5 4,8 10 x SNV 2 2 2 5 4.5 3.5 4 3.5 B. Skin fat 1 x SNV 3 3. 3.5 4.8 4.8 4 4 4 5 x SNV 2.5 3 2.5 3.8 4 4 3.5 4 10 x SNV 2.5 2.5 2.5 3.8 3.8 3.5 4 4 EXAMPLE 4 v The liquors listed in the table which follows are pre- 1 [A"' pared with the substances of Example 3 (amounts CH stated in g/l). I 2

)un Y CH i) coo- I A B 11o- CH2 0 Product from Example 3 6 60 (|:H m I Water Made up I 10 X 1000 ml Acetic acid 40% strength [0 l0 80 so we 40 40 A1c1,.6 1-1 0 2 2 CHPN N CH2 see Example l9 1 H C l Parafl'm emulsion according to Example [8 E HC Y, 2

Pleces of fabr1c of cotton, cotton-polyester, synthet1c n polyamide, polyester and wool gabardine are succes- CH---C- sively dipped into this liquor and thus impregnated with the perfluoro compound. 40

The fabric samples are thereafter dried for 5 minutes (E) R at 130 C. I

The assessment of the oil-repellent effect is carried 83 out as indicated in Example l6 and 18. The results are summarised in the table which follows.

Substrate Rating achieved with Liquors 2q .28 12,2 wherein 5 x SNV 3 R represents perfluoroalkyl with 4 to 14 carbon 9 X SNV 3 atoms, 1 x TR 50 100 E represents cycloalkylene of 5 to 6 carbon atoms, or Cotton/Polyester as obtained n-alkylene of l to 10 carbon atoms, 1 X SNV 3 X and X each re resent meth l or h dro en, 5 x SNV 3 so 90 55 y H 9 x SNV 3 Y and Y each represent hydrogen or methyl, A and l X TR 90 A' each represent the group Polyester as obtained 60 70 1 x SNV 3 so so 5 x SNV 3 60 70 9 x SNV 3 60 C -C 1 x TR 70 so All finishes are also hydrophobic,

wherein The embodiments of the invention in which an exclusive property or privilege is claimed are defined as fol- 65 lows:

l. A pcrfluoroalkylmonocarboxylic acid ester of the formula Z Z Z and 2, each represent hydrogen or alkyl of l to 4 carbon atoms; q is l, and

m, n, p and x eachrepresent l or 2..

2. A compound according to claim 1, wherein E represents n-alkylene of 1-10 carbon atoms.

31 32 3. A compound according to claim 2, wherein .r' in which u is a whole number from 5 to 9 and w is 2 or equals 1. 4.

4. A compound according to claim 3, wherein Y and 11. Perfluoroalkylmonocarboxylic acid ester accord- Y are each methyl, and X and X are each hydrogen. 5 ing to claim 1 of the formula (I'll CH CH 111cm ---c*1---c -I-: Is- -cP--c:1

IIO CH ll 5. A compound according to claim 4, wherein Z Z in which u is 5, 7 or 9. 2;, and Z, are each hydrogen. l2. Perfluoroalkylmonocarboxylic acid ester accord- 6. A compound according to claim 5 wherein n l. ing to claim 1 0f the formula 7. A compound according to claim 6 wherein n 2. 8. Perfluoroalkylmonocarboxylic acid ester according to claim 1, wherein R represents perfluoroalkyl of 5 to ll carbon atoms. 9. Perfluo roalkylmonocarboxylic acid ester according to claim 1, wherein R represents perfluoroalkyl of 7 to 9 carbon atoms CF (CF )COOCH CH CH i CH C C 10. Perfluoroalkylmonocarboxylic acid ester accord- 2 C/ ing to claim 1 of the formula 9 OH 0 CH2C 2 HO- CH A I] o UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,92 9

Pa e 1 f 2 O DATED November 18, 1975 g 0 VENT0R(S) 1 HORST JAEGER it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 0

Column 30, claim 1, lines 21- i8, amend formula (1) to read:

All I Q CH2 N N R-( I i 000- Y ICH O HO- -CH O 0 2 'C CH2 G Alli 1 CH N N CH 2 2 I H C II 0 HC-Y' Q n--l I O r p- CH2 ('3 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,920,6 9 Page 2 of 2 DATED November 18, 1975 |NV ENTOR(S) HORST JAEGER It is certifi ed that eTror appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

E -R' I --'OOC Signed and Sealed this first D3) Of June1976 [sen] Arrest:

RUTH C. MASON Arresting Officer c. MARSHALL DANN Commissioner ofPatenn and Trademarks 

1. A PERFLUOROALKYLMONOCARBOXYLIC ACID ESTER OF THE FORMULA
 2. A compound according to claim 1, wherein E represents n-alkylene of 1-10 carbon atoms.
 3. A compound according to claim 2, wherein x'' equals
 1. 4. A compound according to claim 3, wherein Y and Y'' are each methyl, and X and X'' are each hydrogen.
 5. A compound according to claim 4, wherein Z1, Z2, Z3 and Z4 are each hydrogen.
 6. A compound according to claim 5 wherein n
 1. 7. A compound according to claim 6 wherein n
 2. 8. Perfluoroalkylmonocarboxylic acid ester according to claim 1, wherein R represents perfluoroalkyl of 5 to 11 carbon atoms.
 9. Perfluoroalkylmonocarboxylic acid ester according to claim 1, wherein R represents perfluoroalkyl of 7 to 9 carbon atoms.
 10. Perfluoroalkylmonocarboxylic acid ester according to claim 1 of the formula
 11. Perfluoroalkylmonocarboxylic acid ester according to claim 1 of the formula
 12. Perfluoroalkylmonocarboxylic acid ester according to claim 1 of the formula 